Beta-halogenated unsaturated nitriles



Patented Mar. 16, 1948 UNITED STATES PATENT OFFICE BETA-HALOGENATED UNSATURATED NITRILES Albert M. Cliflord and Joy G. Lichty, Stow, Ohio,

asslgnors to Wing! where X is selected from the group consisting of hydrogen, halogen, alkyl, halo alkyl, aryl, aralkyl, alkoxy and alicyclic radicals, R is halogen and R1 is hydrogen or halogen. Thus, the compounds contain one halogen atom on the beta carbon atom and may contain two halogen atoms in this position or a halogen atom may be present in both the alpha and beta positions, but not more than two such atoms will be present on the alpha and beta carbon atoms together.

The class of new compounds is illustrated by alpha, beta-dichloro acrylonitrile, having the formula CHCl=CCl-CN, this compound being valuable in the formation 01 rubber-like materials by copolymerization with butadiene or with butadiene and another monomeric substance. Other compounds coming within the class are beta chlor acrylonitrile, beta brom acrylonitrile, alpha beta dibrom acrylonitrile, beta beta dichlor acrylonitrile, beta beta dibrom acrylonitrile, alpha brom beta chlor acrylonitrile, alpha chlor beta brom acrylonitrile, alpha methyl beta chloro acrylonitrile cis and trans, alpha methyl beta brom acrylonitrile cis and trans, alpha chloro methyl beta chlor acrylonitrile, alpha methyl beta beta dichlor acrylonitrile, alpha phenyl-beta chlor acrylonitrile, alpha methoxy not Corporation, Akron, Ohio, a corporation of Delaware No Drawing. Application November 29, 1940, Serial No. 367.772

3 Claims. (CL 260-464) beta chlor acrylonitrile, alpha ethyl beta chlor acrylonitrile, alpha chlor ethyl beta chlor acrylonitrile, alpha cyclohexyl beta chlor acrylonitrile. and alpha benzyl beta chlor acrylonitrile. Other compounds embraced by the formula given above are also included. the compounds mentioned being set forth only by way of illustration.

These compounds can be prepared by methods involving removal of hydrogen halide from a trihalo nltrile, by means of a dehydrohalogenating agent. Thus. alpha beta dichloro acrylonitrile may be obtained by removing hydrogen chloride from alpha alpha beta trlchloro propionitrile, the reaction being as follows:

The hydrogen chloride may be removed by treatment with caustic soda or tertiary amines, for example. or it may be removed by pyrolysis of the trichloro propionitrile. The alpha beta dichloro aorylonitrile thus obtained has a boiling point of 59-60 (1/60 mm, a density of and an index oi. refraction The cis and trans alpha-methyl-beta-chloro acryionitriles may likewise be prepared by removing hydrogen chloride from the appropriate saturated nitriles, in this case dichlor isobutyro nitrile. The reaction is as follows CHiCl-CCl-CN -0 CHOhC-CN HCI HI H:

The hydrogen chloride may be removed by treatment with caustic soda or tertiary amines or other hydrogen halide removing agent. It may also be removed by. pyrolysis of the saturated nitrile. This compound may also be prepared by pyrolyzing the acetylated cyanohydrin oi chlor acetone to remove acetic acid. The two forms of this compound obtained are distinguished but not identified by the following 3 physical characteristics: Boiling point 155-158 (2.. density D2} 1.0920 and index or refraction N1: 1.4584 and boiling point 126-128 0.. density Di: 1.0762 and index oi refraction The halogen analysis compares closely with the theoretical.

The class oi compounds set forth herein may be useful in the formation of plastic masses either by themselves or when copolymerized with other monomeric substances. Thus, they may be ccpolymerized with 1,3-butadiene or with substituted butadienes, such as isoprene. 2-3-dimethy1 1.3-butadiene, chioroprene, dichlor butadiene and the like. They may also be copolymerized with various esters of acrylic acids such as methyl acrylate. methyl methacrylate, ethyl acrylate, ethyl methacrylate. diethyl itaconate. dipropyl itaconate, dibutyl itaconate, dichloroacrylates, dibromacrylates, and the like. Copolymers are also obtained with various acrylonitriies such as acrylonitrile, methacrylonitrile and ethacrylonltrile. The nitriles and the esters oi acrylic acids may be generally termed saponiflable derivatives of acrylic acids. Furthermore, rubber-like materials have been obtained from three component copolymers including one of the above described class of beta-haio-acrylonitriles. a butadiene and an ester or a nitrile oi an acrylic acid.

Rubber-like copolymers were prepared from certain of the foregoing beta halo acrylonitriles by placing the monomers in selected proportions in a glass-lined container in an emulsion including an emulsifying agent, such as 6% Duponol. a buffer such as phosphate-citrate and a catalyst such as carbon tetrachloride. The oxygen is removed i'rom the free space above the emulsion and the polymerization carried on at a temperature of 38 C. with agitation. Some of the results obtained are as follows:

It will be noted that plastic materials having good tensile strength and elongation and modulus satisfactory for a rubber-like product were obtained.

A series or polymerizations were also carried out with mixtures of one o! the alpha methyl beta chloroacrylonitriles and butadiene, the mixture containing 40% of the nitrile and 60% of butadiene. The emulsion used was made up as follows:

Per cent TRANS (T) ALPHA-M ETHYL-BETA-OHLOR OACRYL- ONITRILE 015 (f) ALPHA-METHYL]!ETA-CHLOROAORYL- ONITRILE 6 days 44.

ing the structural formula Monomers Ratio pH g? Yield Properties 15 6.6 42 bill Buiadienc o Diehloroau'ylonitrile 40 4 Butadieno so Dichloroacrylonitrile 40 n u fi:fi: a;""% Butadiene 70 Town" Diohloroacrylonitrile 31 Butadieno 8D Dlchloroacrylonitrile a0 W i Buiadiono n-Bu-methacrylate 16 96 23 78 Dichloroacrylonitrilm 15 I 70 ensils Ethyl methaa-ylate. 15 5.7 28 72 Dichloroacrylonltrile i5 Modul Butadiene d0 'Iensi Dlbutylitaoonate 20 8.1 z; 81 Dlchloroacrylouitril 20 Bntadiene o0 Dimethyl itaconnte... 20 7.6 23 86 Elena... ".515 Dlchloroacrylonitrile- 20 Modulus .1011 Butadiene Me-chloroa Iate 20 6.1 18 81.9 Dichloroacry onltrile 20 5 6 wherdnZiaahulogenatomandR-Isarsdlcall Number Home Beta of the group consisting of alkyl. halo alkyl, ml, 2,210,820 Kautter Aug. 6, 1940 aralkyl, and elkoxy radicals. 1, 2 Hab wd Feb. 11, 1941 ALBERT M, 31mm 4 ,54 Pollack June 10. 41 JOY G 11cm 5 3,393,739 Llchty Oct. 13, 1942 2,828,984 Llchty Sept. '1, 1943 REFERENCES CITED OTHER REFERENCES The llowin r e e c s re of record in the Lespieau: Compt. rendus, vol. 130, page 1410 file or this patent: m (1900), 3 3 1 UNITED STATES PATENTS natal-hr. Berlchte. vol. 4 pages 04 -3045 Number Name Date Boeseken et 9.1.: Rec. des trav. Chim.. vol. 32,

2,021,763 Bauer et a1 Nov. 19, 1935 page 101 (1911). 2,174,758 Pleroh Oct. 3, 1939 Certificate of Correction Patent No. 2,437,998. March 16, 1948. ALBERT M. CLIFFORD ET AL.

It is hereby certified that error appears in the printed specification of the above numbered patent requiring correction as follows:

Column 4, line 22, in the table, first column thereof, for 7.80 read 7.0;

and that the said Letters Patent should be read with this correction therein that the same may conform to the remrd of the case in the Patent Office.

Signed and sealed this 12th day of April, A. D. 1949.

THOMAS F. MURPHY,

Assistant Commissioner of Patents.

5 6 wherdnZiaahulogenatomandR-Isarsdlcall Number Home Beta of the group consisting of alkyl. halo alkyl, ml, 2,210,820 Kautter Aug. 6, 1940 aralkyl, and elkoxy radicals. 1, 2 Hab wd Feb. 11, 1941 ALBERT M, 31mm 4 ,54 Pollack June 10. 41 JOY G 11cm 5 3,393,739 Llchty Oct. 13, 1942 2,828,984 Llchty Sept. '1, 1943 REFERENCES CITED OTHER REFERENCES The llowin r e e c s re of record in the Lespieau: Compt. rendus, vol. 130, page 1410 file or this patent: m (1900), 3 3 1 UNITED STATES PATENTS natal-hr. Berlchte. vol. 4 pages 04 -3045 Number Name Date Boeseken et 9.1.: Rec. des trav. Chim.. vol. 32,

2,021,763 Bauer et a1 Nov. 19, 1935 page 101 (1911). 2,174,758 Pleroh Oct. 3, 1939 Certificate of Correction Patent No. 2,437,998. March 16, 1948. ALBERT M. CLIFFORD ET AL.

It is hereby certified that error appears in the printed specification of the above numbered patent requiring correction as follows:

Column 4, line 22, in the table, first column thereof, for 7.80 read 7.0;

and that the said Letters Patent should be read with this correction therein that the same may conform to the remrd of the case in the Patent Office.

Signed and sealed this 12th day of April, A. D. 1949.

THOMAS F. MURPHY,

Assistant Commissioner of Patents. 

